Process of combining hardenable phenol-aldehyde condensation products with air-drying fatty oils



Patented Apr. 14, 1942 UNITED STATES PATENT OFjFlCE" PROCESS OF COMBINING HARDENABLE PHENOL ALDEHYDE CONDENSATION PRODUCTS WITH AIR-DRYING FATTY OILS Fritz Seebach, Erkner, near Berlin, Germany, assignor, by mesne assignments, to Bakelite v Corporation, a corporation of New Jersey No Drawing. Application February 12, 1930, Serial No. 427,993. In Germany February 25,

6 Claims.

Resoles, i. e. synthetic resinous products of a hardenable nature in their fusible and-soluble initial condition, and air-drying, fatty oils cannot be mixed or are insoluble in each other. This "constitutes a serious disadvantage, for resoles .ably changed in imparting the oil-soluble property thereto. The obtained products show a novolak character, that is, they remain fusible and soluble under the application ofheat, and they can as a result be combined with oils at the usual high temperatures employed in the lacquer or varnish practice. However, if the resole character is to be retained such methods of working are out of the question on account of the readily initiated conversion of theresoles to their infusible and'insoluble condition which takes place under application of heat. It has been proposed to simplymix a resole with an airdrying oil in a common solvent at temperatures which do not cause transformation oi! 'the resole. As a matter of fact such solutions are readily obtained; but a separation of oil and resole takes place to a degreecorresponding to the evaporation of the solvent either'from a coating made with the solution or from the solution.

We have now foundthat air-drying oils which are in some manner combinedwith more 'or less I oxygen show an entirely different behavio'r[towards resoles. Air-drying fatty oils, for example', which contain a small proportion of their own oxidation products in solution, or which have undergone a mild oxidation throughout their mass, may be incorporated with resoles in any proportion and used in lacquers'to yield surfaces that remain glossy. The composite oil and resole products have the surprising property of solution in or dilution with solvents that are otherwise non-solvents for one of the two components, either the oil or the'resole. For instance, a varnish made with such products can be diluted with turpentine aloneor with wood alcohol alone. Films deposited therefrom are hardenable to an exceptional degree. They are resistant to mechanical and chemical influences; as an instance they are not changed ,when sub- Jected for days to the action of organic solvents such as benzene-alcohol, etc.

Resales for incorporation. with air-drying oils according to this invention can be produced in any suitable manner, for example, by-the condensation of phenol or cresol with an aldehyde such as formaldehyde, using ammonia as a condensing agent. Resoles'made by the addition of hardening agents to novolaks can be used, or a mixture of several resoles. Suitable air-drying oils are linseed oils, China wood oil, perilla oil, poppyseed oil, linseed-stand oil or mixtures of these oils. Oxidation of these oils can be accomplishedin the usual manner, for example, by the action of air at ordinary or, elevated temperatures, simple exposure to the air, short-wave rays, ozonization, etc.'-. Several air-drying oils 7 can 'be mixed together and then oxidized or the or a suitable solvent mixture at ordinary'tem-j peratures. Coatings obtained with such oil var-- nishes remain glossy under all conditions, whether they be air dried or hardened by heat at elevated temperatures, and therefore exceptionally desirable. A similar mixture in solutioncontaining linseed oil varnish instead of linoxin would upon air drying as well in hardening by heat become turbid and therefore not usable. With the use of air-drying fatty oils which are oxidized to but a small percmtage of their oxygen absorbing capacity it is generally not 'sufllcient to mix resoles with them in any kind of solvent at ordinary temperatures: in such cases bothcompcnents should be heated for some time and preferably in .the presence of a diluting,

agent. The heating temperature and the-heating period may be decreased in proportion to the increased absorption'ofoxygen by the air-dryin oil. The combination of air-drying fatty oils with resoles can be'hastened by the presence of certain catalysts, such'aslead oxide. Catalysts are especially desirable if the air-drying oils contain but a small amount of oxidation products. For example, resoles can be combined with linseed oil or the like by boiling the'oil with a solution of the resole in'the presence of oxygen bearins catalysts, such as lead oxide, manganese oxide, etc., or combinations ofthese substances with fatty oils or resins. Several catalysts can be used in admixture or twoor more of them used consecutively. The quantity of catalyst to with be added varies with the different oils. linseed oils, for-example, more catalyst is re- 1 part by weight of a solvent dissolving both subin the air and after hardening on metal yield --mixture and it yields "clear drying and clear Resole prepared from technical cresol Solvents as per Example 1..

-'under avacuum. The residue is bright and i l-part by weight of a resole prepared by con- 5 ,densation. 1 part by weight of an air-blown linseed oil.

' stances equally well, for example, cyclohexanol or a 1:1 mixture of turpentine and wood alcohol or a 1:1 mixture of benzolwood alcohol.

are heated for or hour at 80-100"C. Then the volatile ingredients are removed under a vacuum while the temperature should not exceed 100'. .After removal of the'volatile ingredients a substance is obtained that is extremely tough at room temperature, yet perfectly clear, consisting of about equal proportions of resole and fatty oil. The product in this consistency is similar to softer kinds of resoles and in appearance is hardly to be distinguished from them.

The clear solubility of the product in wood alcohol or in oil of turpentine is remarkable. The

films obtained from such solutions quickly dry elastic coatings resistant to organic solvents, such as carbon disulfide.

Example 2 Theprocedure is the same as in Example 1, however, instead of air-blown linseed oil a mixturefof equal portions 'of'ordinary China wood oil and air-blown linseed oil are-applied. The finished product is clearly soluble in oil 0 turpentine or in an oil of turpentine-wood alcohol hardening films.

' Ezample-ti Parts y condensation with formaldehyde and ammonia 50 Solvents as per'Example 1 50 standeoil of airblown linseed oil 12 are heated to 100 C. for 1% hours or %.hour to 160 if desired under pressure, and the solvent "is driven off under a vacuum. The finished product is soluble in wood alcohol or in a mixture of wood alcohol and turpentine.

Example f Parts Hardenable condensation products from v cresol, formaldehyde and ammonia '15 Linseed oil varnish Lead oxide or tjparts man se ,oxide 6 are heated to 120 Clfor l'hoiirfif desired under pressure. Then the'volatile solvent is driven oil! easily soluble in a turpentine-wood alcohol mixture. In the oils, which. as specified in the example, are to be combined with the resoles one may dissolve other resins also, as for example,

' natural resins or synthetic resins and proceed analogous 'to the above examples. One may however dissolve in the oils such substances also that ordinarily do not combine with hardenable phenol condensation products, as for example, caoutchouc.

Example 5 Parts by weight Hardenable phenol-aldehyde condensation products 2 Melt of oxidized linseed oil and caoutchouc in the proportion of 1:1 2

Solvents according to Example 1 4 are heated together at a temperature of 100l30 C. until the fusion is completed. The films thus produced ar bright. The varnishes or films may be vulcanized.

One may also obtain molded parts from the combination products of hardenable phenolaldehyde condensation products and air-drying cils by charging the molds with the heated product if desired after admixture with fillers. dyes or other, suitable additions and by hardening for example at temperatures of -150" C. Perfectly clear, hard, elastic substances can thus be obtained The products obtained according to the invention may furthermore be used for impregnation. superposed layers of paper, that is, for example, saturated with a wood alcohol solution of the described combination products from resoles and air-drying oils may be molded under heat and pressure into solid pieces. Instead of a single solvent one may in this instance as in all the others use suitable solvent mixtures in the preparation and application of the combination products.

I claim:

,1. Process of preparing compositions which comprises mixing a hardenable phenol-aldehyde condensation product with an oxidized air-drying fattyoil in a solvent for both components and thereafter removing the solvent.

2. Process of preparing compositions which comprises mixing a hardenable phenol-aldehyde condensation product with an oxidized air-drying fatty oilina solvent for bothcomponents and thereafter removing the solvent under-reduced pressure.-

3. In a process of preparingcompositions from hardenable phenol-aldehyde condensation products and air-drying fatty oils the step which comprises oxidizing an air-drying fatty oil in the presence of the hardenable phenol-aldehyde condensation product.

4.-In a process of preparing compositions from hardenable phenol-aldehyde condensation products and air-drying fatty oils the step which comprises oxidizing an air-drying fatty oil in the presence of the hardenable phenol-aldehyde condensation product, said condensation product being distributed as a suspensionin the oil.

5. Process of preparing compositions which comprises mixing hardenable phenol-aldehyde condensation product with an oxidized air-drying fatty oil in a solvent for both components and with .the application of heat, and thereafter removinsthe solvent.

condensation product with an oxidized air-drying fatty oil in a solvent for both tfimponents and with the application of heat, and'thereafter removing the solvent under reduced pressure.

FRITZ SEEBACH.

murmu- OI" CORRECTION intent Io. 2,279.1;99. April 1h, 19m.

FRITZ SEEBACH. It 1; hreb eertifledthat error appears in the printed specifica tion bf'the, abeve. numbered patant rquiring corr'ecfiidnias follows; Page 2, second column, line 69, claim 6,1or phenoj-aldehyde read -'--phehd1-'aldehyde-j--; and that the said Letters Patent should be read with this cor I e c tion than in that the same may confom to the recordjof the cas ihfihTatnt Signed and sealed this 16th day of June, A. p. 1913.,

Hem-y van Arsdale, (Seal) A Acting Commissioner of Patehta. 

